Fungicidal compositions and methods



United States Patent 3,345,258 FUNGICIDAL COMPOSITIONS AND METHODS HarryA. Sidles, Wheaton, Ill., assignor to Velsicol Chemical Corporation,Chicago, Ill., a corporation of Illinois No Drawing. Filed Aug. 9, 1965,Ser. No. 478,431 15 Claims. (Cl. 167-39) This invention relates to newfumigant compositions having high residual activity. In particular thisinvention relates to compositions containing methyl bromide andinsecticidally and fungicidally active materials and a method ofapplying them to the soil. Methyl bromide has been known for many yearsto be an extremely effective fumigant. It is extremely effective againsta variety of insects, nematodes, weeds and fungi. It is used to fumigatewarehouses, plants, mills and other buildings. It is particularly usedto fumigate bulk grain. In addition it can be used as a soil fumigant. 7

While methyl bromide is extremely eifective as a fumigant and it givesrelatively instantaneous results because it is a gas at normal roomtemperatures and pressures, it does not have appreciable residualactivity. Thus, while it does give an excellent short-term protectionagainst insects, weeds, fungi, it is relatively poor for protectingareas for long periods of time.

It is, therefore, an object of the present invention to provide aneffective fumigant having improved residual eifect.

It is a further object of the present invention to provide short-termand residual protection against pests and undesirable plant life in asingle application.

It is still another object of the present invention to providecompositions that will provide this short and long-term protectionwithout the need for extensive amounts of inert carrier material.

It is still another object of the present invention to providecompositions which will give the desired protection on a uniform basis.

It is still another object of the present invention to devise a methodfor protecting plants from infestation and infection for a substantialtime interval by a single application.

Other objects of the present invention will become apparent from theensuing description.

It has now been found that compositions containing a major amount ofmethyl bromide and in addition containing a residual insecticide and aresidual fungicide can be easily prepared. These compositions comprisingthe present invention containas their active components methyl bromidein combination with residual fungicides and residual insecticides..Since methyl bromide is an odorless and somewhat hazardous material, itis normal to include in compositions containing it a warning agent. Oneof the most widely used warning agents is chloropicrin. This warningagent is normally present in amounts of about 1 or 2% by weight of themethyl bromide. Other warning agents can be used.

The ratio of the three active ingredients present in the compositionswill vary with their identity and with the application for which thecomposition is being prepared. The reason for this is that variousinsecticides and fungicides will have different effectiveness andaccordingly will require varied amounts to provide adequate protection.

Among the insecticides which can be used in these compositions are thechlorinated hydrocarbons including chlordane, heptachlor, aldrin, anddieldrin. Other insecti cides are also useful for specific purposes.

A variety of fungicidally active materials can be used in thesecompositions. As in the case with the insecticides, their selection willdepend upon the material being protected. Among the fungicidally activematerials useful are the mercurial fungicides such as mercuric chloride,mercurous chloride, N-methylmercuri-l,2,3,6-tetrahydro- 3,6 endomethano3,4,5,6-,7,7 hexachlorophthalimide, N ethylmercuri1,2,3,6-tetrahydro-3,6-endomethano-3, 4,5,6,7,7 hexachlorophthalimide, Nphenylmercuri-1,2, 3,6 tetrahydro 3,6 endomethano3,4,5,6,7,7-hexachlorophthalimide, N (ethylmercuri)-p-toluenesulfonanilide, methylmercuric dicyandiamide, phenylmercury urea, phenylmercuricacetate and hydroxymercurichlorophenol; pentachloronitrobenzene;dithiocarbamate fungicides such as diammoniumethylenebisdithiocarbamate, ferric dimethyl dithiocarbamate, manganousethylenebisdithiocarbamate, disodium ethylenebisdithiocarbamate, sodiumN methyldithiocarbamate, zinc ethylenebisdithiocarbamate and zincdimethyldithiocarbamate; organic copper fungicides such as: copper8-hydroxyquinolinate, and copper naphthenate; andN-trichloromethylmercapto-4-cyclohexene-LZ-dicarboximide.

In selecting the insecticidal and fungicidal components of the presentcompositions it is important that they possess appreciable residualactivity. This is true of most commercial insecticides and fungicidesparticularly those indicated above.

The amounts of the specific components of the present compositions asindicated above will vary appreciably depending upon the ultimate use ofthe composition. It must be kept in mind that in the presentcompositions different amounts of the methyl bromide, insecticide andfungicide are required for a given application and since all are beingapplied in a single application, the ratios of the components must beselected in accordance with the amounts of materials required to beapplied to the area. For most applications the composition can containfungicide in an amount by weight of from about 0.05 to 10% of the methylbromide content. The insecticidal component can also be present in anamount by weight from about 0.05 to 10% by weight of the methyl bromide.For most applications the content of the insecticidal and fungicidalcomponent can be from about 0.1 to 5% by weight of the methyl bromide.The organic mercurial fungicides need be present in many applications inrelatively low concentrations. Normally it is sufficient that it bepresent in an amount from about 0.1 to 1% by weight of the methylbromide.

Since methyl bromide is a gas at normal temperatures, it is applied frompressure containers. Procedures used for preparing methyl bromidecontainers can be used in preparing the present formulations. This canbe readily accomplished by lowering the methyl bromide tov a temperaturewhereat it is a liquid. Temperatures of from about 10 to 20 C. areadequate.

Once the methyl bromide is in the liquid form the other components ofthe compositions can be readily dispersed in it. These components wouldof course include the insecticidally active material, the fungicidallyactive material and the warning agent such as chloropicrin. Thissolution is then placed in a suitable container from which it can bedischarged as a vapor. It can be seen from this that by using thepresent compositions there is no need for inert diluent. The methylbromide in fact acts as a diluent and dispersant for the othercomponents. This eliminates the use of inactive components and maximizesthe use of the available container space.

In certain instances it is advantageous to utilize a solvent for theresidual fungicide and/or the residual insecticide. The use of thissolvent can be of value in improving the uniiorm application ofmaterials having low solubility in methyl bromide. It is not required bythe present invention that these solvents be employed and it is apreferred feature of this invention that they not be present. When anauxiliary solvent is used it preferably will constitute a smallpercentage of the total composition, although larger amounts can beused.

The selection of the solvent will vary with the identity of thefungicide and insecticide. Compounds known to be useful solvents forthese materials can be employed for this purpose. Exemplary of thesesolvents are the higher boiling alcohols, such as diacetone alcohol andcarbitol; mineral spirits; and aromatic solvents, such as benzene,toluene, etc. which are particularly useful for the organic mercurialfungicides, the aromatic solvents also being useful in preparingsolutions of pentachloro- 'nitrobenzene, the organic copper fungicidesand the chlorinated hydrocarbon insecticides.

It has also been found that unusually uniform application of thecomponents is obtained from these formulations. The release of themethyl bromide from the container disperses with it the other componentsin uniform lamounts over the protected area. This uniformity is noteasily obtained by other means, particularly by a single application.

Applications of these formulations possess residual activity notpossessed by methyl bromide alone. Accordingly, areas treated with thisformulation have superior plant growth over a substantial period oftime. It has alsso been found that these formulations remain in theupper layers of the soil where they are best able to protect the areafrom infestation. Soils treated with the present combination showedlarger plants, more plants and a greener color plant than areas treatedwith methyl bromide alone.

Many formulations can be used by the foregoing procedure and as areillustrated by the following examples:

Example 1 Chlordane (4.5 g.), N-methylmercuri-1,2,3,6-tetrahydro3,6-endomethano-3,4,5,6,7,7-hexachlorophthalirnide .[1.1 g. in diacetonealcohol (6.6 g.)] and chloropicrin procedure of Example 1.

Example 2 Components: Parts by wt.

N methylmercuri-1,2,3 ,6-tetrahydro-3 ,6-endomethano 3,4,5,6,7,7hexachlorophthalimide 0.25 Heptachlor 0.50 Chloropicrin 1.00 Methylbromide 98.25

Example 3 Components:

N methylmercuri-l,2,3,6-tetrahydro-3,6-endomethano 3,4,5,6,7,7hexachlorophthalimide 0.25 Aldrin 0.50 Chloropicrin 1.00 Methyl bromide98.25

Example 4 Components:

N methylmercuri-1,2,3,6-tetrahydro-3,6-endomethano 3,4,5,6,7,7hexachlorophthalimide 0.25

Dieldrin 0.50 Chloropicrin 1.00 Methyl bromide 98.25

4 Example 5 Components: Parts by wt. Pentachloronitrobenzene 2.00Chlordane 1.00 Chloropicrin 1.00 Methyl bromide 96.00

Example 6 Components:

Pentachloronitrobenzene 2.00 Heptachlor 0.50 Chloropicrin 1.00 Methylbromide 96.50

Example 7 Components:

Pentachloronitrobenzene 2.00 Aldrin 0.50 Chloropicrin 1.00 Methylbromide 96.50

Example 8 Components:

Pentachloronitrobenzene 2.00 Dieldrin 0.50 Chloropicrin 1.00 Methylbromide 96.50

Example 9 Components:

N-trichloromethylmercapto-4-cyclohexene-1,2-

dicarboximide 1.00 Chlordane 1.00 Chloropicrin 1.00 Methyl bromide 97.00

Example 10 Components:

Zinc ethylenebisdithiocarbamate 1.00 Heptachlor 0.50 Chloropicrin 1.00Methyl bromide 97.50

Example 11 Components:

N methylmercuri-l,2,3,6-tetrahydro-3,6-end0- methano 3,4,5,6,7,7hexachlorophthalimide 0.05 Chlordane 1.50 Chloropicrin 1.00 Methylbromide 97.45

Example 12 Components:

N ethylmercuri 1,2,3,6-tetrahydro-3,6-endomethano 3,4,5,6,7,7hexachlorophthalimide 0.50 Chlordane 0.05 Chloropicrin 1.5 0 Methylbromide 97.95

Example 13 Components:

Manganous ethylenebisdithiocarbamate 0.10 Aldrin 1.20 Chloropicrin 1.60Methyl bromide 97.10

Example 14 Components:

Ferric dimethyl dithiocarbarnate 0.05 Heptachlor 9.00 Chloropicrin 1.00

Methyl bromide 89.95

Example I 5 Components: Parts by wt. Disodium ethylenebisdithiocarbamate8.00 Aldrin 2.50 Chloropicrin 1.50 Methyl bromide 88.00

It can be seen from this that a variety of compositions of variedamounts of components can be prepared in accordance with the presentinvention.

While the present compositions are useful in protecting a variety ofareas, one of its more important uses is in the protection of tobaccoseed beds. Tobacco seed beds are areas where tobacco seedlings are grownfor transplanting into tobacco fields. These seedlings are quite open toattack by a variety of pests. It has been found that the presentcompositions are particularly advantageous in providing this protection.Protection of other seedlings for transplanting can also be accomplishedby use of these compositions.

I claim:

1. A composition which consists substantially of methyl bromide,residual fungicide in a content of about 0.05 to by weight of methylbromide and a residual chlorinated hydrocarbon insecticide selected fromthe group consisting of chlordane, heptachlor, aldrin and dieldrin in acontent of about 0.05 to 10% by weight of methyl bromide.

2. A composition which consists substantially of methyl bromide,residual mercurial fungicide in a content of about 0.05 to 10% by weightof methyl bromide and a residual chlorinated hydrocarbon insecticideselected from the group consisting of chlordane, heptachlor, aldrin anddieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

3. A composition which consists substantially of methyl bromide,residual dithiocarbamate fungicide in a content of about 0.05 to 10% byweight of methyl bromide and a residual chlorinated hydrocarboninsecticide selected from the group consisting of chlordane, heptachlor,aldrin and dieldrin in a content of about 0.05 to 10% by weight ofmethyl bromide.

4. A new composition which consists substantially of methyl bromide,N-methylmercuri-l,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide in a content of about 0.05to 10% by weight of methyl bromide and chlordane in a content of about0.05 to 10% by weight of methyl bromide.

5. A new composition which consists substantially of methyl bromide, Nethyhnercuri 1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide in a content of about 0.05to 10% by weight of methyl bromide and chlordane in a content of about0.05 to 10% by weight of methyl bromide.

6. A composition which consists substantially of methyl bromide,pentachloronitrobenzene in a content of about 0.05 to 10% by weight ofmethyl bromide and a residual chlorinated insecticide selected from thegroup consisting of chlordane, heptachlor, aldrin and dieldrin in acontent of about 0.05 to 10% by weight of methyl bromide.

7. A method for the protection of plants against infestation andinfection which comprises applying to the soil of the plants aneffective amount of the composition of claim 6.

8. A composition which consists substantially of methyl bromide,N-methylmercuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimidein a content of about 0.05 to 10% by weight of methyl bromide and aresidual chlorinated hydrocarbon insecticide selected from the groupconsisting of chlordane, heptachlor, aldrin and dieldrin in a content ofabout 0.05 to 10% by weight of methyl bromide.

9. A composition which consists substantially of methyl bromide,residual organic copper fungicide in a con- 6 tent of about 0.05 to 10%by weight of methyl bromide and a residual chlorinated hydrocarboninsecticide selected from the group consisting of chlordane, heptachlor,aldrin and dieldrin in a content of about 0.05 to 10% by weight ofmethyl bromide.

10. A composition which consists substantially of methyl bromide,N-trichloromethylmercapto-4-cycl-ohexene- 1,2-dicarboximidein a contentof about 0.05 to 10% by weight of methyl bromide and a residualchlorinated hydrocarbon insecticide selected from the group consistingof chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05to 10% by weight of methyl bromide.

11. A method for the protection of plants against infestation andinfection which comprises applying to the soil of the plants aneffective amount of a composition comprising methyl bromide, residualfungicide in a content of about 0.05 to 10% by weight of methyl bromideand a residual chlorinated hydrocarbon insecticide selected from thegroup consisting of chlordane, heptachlor, aldrin and dieldrin in acontent of about 0.05 to 10% by weight of methyl bromide.

12. A method for the protection of plants against infestation andinfection which comprises applying to the soil of the plants aneffective amount of a composition comprising methyl bromide, residualmercurial fungicide in a content of about 0.05 to 10% by weight ofmethyl bromide and a residual chlorinated hydrocarbon insecticideselected from the group consisting of chlordane, heptachlor, aldrin anddieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

13. A method for the protection of plants against infestation andinfection which comprises applying to the soil of the plants aneffective amount of a composition comprising methyl bromide,N-methylmercuri-l,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7hexachlorophthalimide in a content of about 0.05 to 10% by weight ofmethyl bromide and a residual chlorinated hydrocarbon insecticideselected from the group consisting of chlordane, heptachlor, aldrin anddieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

14. A method for the protection of plants against infestation andinfection which comprises applying to the soil of the plants aneffective amount of a composition comprising methyl bromide, residualdithiocarbamate fungicide in a content of about 0.05 to 10% by weight ofmethyl bromide and residual chlorinated hydrocarbon insecticide selectedfrom the group consisting of chlordane, heptachlor, aldrin and dieldrinin a content of about 0.0 to 10% by weight of methyl bromide.

15. A method for the protection of plants against infestation andinfection which comprises applying to the soil of the plants aneffective amount of a composition comprising methyl bromide, residualorganic copper fungicide in a content of about 0.05 to 10% by weight ofmethyl bromide and a residual chlorinated hydrocarbon insecticideselected from the group consisting of chlordane, heptachlor, aldrin anddieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

References Cited UNITED STATES PATENTS 2,598,562 5/1962 Kleiman 260-326OTHER REFERENCES Frear: Pesticide Index (1963), College SciencePublishers, PO. Box 798, State College, Pa., pp. 16, 47, 51, 123,156 and181.

Thorn: The Dithiocarbamates and Related Compounds (1962), ElsevierPublishing Co., New York, pp. 3 and 4.

Frear: Pesticide Index (1961), p. 132.

ALBERT T. MEYERS, Primary Examiner. JULIAN S. LEV-ITT, Examiner. STANLEYJ. FRIEDMAN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,345,258 October 3, 1967 Harry A. Sidles It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 3, line 25, for "alsso" read also column 6, line 48 for "0 0"read 0 .05

Signed and sealed this 15th day of October 1968.

(SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attcsting Officer

1. A COMPOSITION WHICH CONSISTS SUBSTANTIALLY OF METHYL BROMIDE,RESIDUAL FUNGICIDE IN A CONTENT OF ABOUT 0.05 TO 10% BY WEIGHT OF METHYLBROMIDE AND A RESIDUAL CHLORINATED HYDROCARBON INSECTICIDE SELECTED FROMTHE GROUP CONSISTING OF CHLORDANE, HEPTACHLOR, ALDRIN AND DIELDRIN IN ACONTENT OF ABOUT 0.05 TO 10% BY WEIGHT OF METHYL BROMIDE.